Amorphous propylene-ethylene copolymers

ABSTRACT

Amorphous propylene-ethylene copolymers are described herein that can include high amounts of ethylene and exhibit desirable softening points and needle penetrations. The desirable combinations of softening points and needle penetrations in these propylene-ethylene copolymers allow them to have a broad operating window. Due their broad operating window, the propylene-ethylene copolymers can be utilized in a wide array of applications and products, including hot melt adhesives.

BACKGROUND

1. Field of the Invention

The present invention is generally related to amorphouspropylene-ethylene copolymers and processes for producing suchcopolymers. More particularly, the present invention is generallyrelated to amorphous propylene-ethylene copolymers having desirableneedle penetrations, softening points, viscosities, and viscoelasticcharacteristics.

2. Description of the Related Art

Amorphous polyolefins are commonly used in industry to produce a widearray of products including, for example, adhesives. Common polyolefinsutilized in adhesives generally include copolymers produced frompropylene, ethylene, and various C₄-C₁₀ alpha-olefin monomers, such as,for example, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, and 1-decene. In particular, propylene-butene copolymers arecommonly used to produce hot melt adhesives due to the higher adhesivebond strengths derived from these copolymers. Much of the adhesive bondstrength derived from these copolymers can be attributed to the C₄-C₁₀alpha-olefins contained therein, which can greatly increase thesubsequent bonding properties of the copolymer. Unfortunately, C₄-C₁₀alpha-olefins can be quite expensive due to market availability and canalso exhibit limited reactivity during the polymerization processes.

Due to the above deficiencies of the C₄-C₁₀ alpha-olefins, somemanufacturers have attempted to replace C₄-C₁₀ alpha-olefins withethylene. Unlike many of the C₄-C₁₀ alpha-olefins, ethylene can be morereadily available and more reactive than many of the commonly usedC₄-C₁₀ alpha-olefins, such as 1-butene. Unfortunately,propylene-ethylene copolymers can exhibit deficiencies in hardness,thereby resulting in adhesives that lack ideal bond strength over time.Some manufacturers have attempted to increase the hardness of thesecopolymers by incorporating crystalline polypropylene therein. However,by adding crystalline polypropylene to these copolymers, the softeningpoints of the copolymers are also increased. This can limit theapplication of these copolymers to certain types of adhesives due to thehigher softening points.

Thus, there is a need for amorphous copolymers that exhibit an idealbalance between hardness and softening point and that can also be usedto produce adhesives with improved adhesive characteristics.

SUMMARY

One or more embodiments of the present invention concern a copolymercomprising propylene and ethylene, which has a softening point in therange of 90 to 140° C. Furthermore, the copolymer has a needlepenetration that is equal to y, which is defined by the followingformula:

y≦0.000000262249x6+0.000172031278x5−0.046669720165x4+6.701746779438x3−537.286013331959x2+22,802.983472587x−400,204.018086126

In the above formula, x is the softening point of the copolymer.

Additionally, one or more embodiments of the present invention concern acopolymer comprising propylene and ethylene. The copolymer has asoftening point in the range of 110 to 135° C. and a needle penetrationof less than 25 dmm.

Furthermore, one or more embodiments of the present invention concern acopolymer comprising propylene and ethylene. The copolymer has asoftening point in the range of 90 to 121° C. and a needle penetrationof less than 35 dmm.

Also, one or more embodiments of the present invention concern acopolymer comprising propylene and ethylene. The copolymer has asoftening point in the range of 90 to less than 115° C. and a needlepenetration equal to or less than 53 dmm.

Moreover, one or more embodiments of the present invention concern a hotmelt adhesive. The hot melt adhesive comprises a copolymer comprisingpropylene and ethylene. The copolymer has a softening point in the rangeof 90 to 140° C. and a needle penetration that is equal to y, which isdefined by the following formula:

y≦−0.000000262249x6+0.000172031278x5−0.046669720165x4+6.701746779438x3−537.286013331959x2+22,802.983472587x−400,204.018086126

In the above formula, x is the softening point of the copolymer.

In addition, one or more embodiments of the present invention concern aprocess for producing a copolymer. The process comprises reactingpropylene and ethylene in the presence of a catalyst system comprisingan electron donor to form the copolymer. The copolymer has a softeningpoint in the range of 90 to 140° C. and a needle penetration that isequal to y, which is defined by the following formula:

y≦−0.000000262249x6+0.000172031278x5−0.046669720165x4+6.701746779438x3−537.286013331959x2+22,802.983472587x−400,204.018086126

In the above formula, x is the softening point of the copolymer.

In yet further embodiments of the present invention, a process forproducing a copolymer is provided. The process comprises reactingpropylene and ethylene in the presence of a catalyst system comprisingan electron donor to form the copolymer. The copolymer has a softeningpoint in the range of 110 to 140° C. and a needle penetration that isequal to y, which is defined by the following formula:

y≦−0.000751414552642x ⁴+0.374053308337937x ³−69.5967657676062x²+5,734.02599677759x−176,398.494888882

In the above formula, x is the softening point of the copolymer.

BRIEF DESCRIPTION OF THE FIGURES

Embodiments of the present invention are described herein with referenceto the following drawing figures, wherein:

FIG. 1A depicts the viscoelastic characteristics of particularpropylene-ethylene copolymers produced in Example 1;

FIG. 1B depicts the viscoelastic characteristics of particularpropylene-ethylene copolymers produced in Example 1;

FIG. 2 depicts the viscoelastic characteristics of the adhesivesproduced in Example 4;

FIG. 3 depicts the viscoelastic characteristics of the adhesive producedin Example 5; and

FIG. 4 depicts the viscoelastic characteristics of the adhesivesproduced in Example 6.

DETAILED DESCRIPTION

The present invention is generally related to amorphouspropylene-ethylene copolymers and their various applications. Many ofthe existing propylene-ethylene copolymers in the market today generallyexhibit deficiencies regarding their softening points or hardness. Theinventive copolymers described herein exhibit improved propertiescurrently not available in these commercial copolymers. In particular,as described below in further detail, the inventive copolymers canexhibit desirable softening points and needle penetrations, therebyresulting in copolymers that are useful in a wide array of applications.

The Propylene-Ethylene Copolymers

Commercially-available propylene-ethylene copolymers have generally notbeen strong enough to be used in adhesives for packaging applications orhygiene products (e.g., diapers and feminine care products). Generally,this has to do with the lack of balance between the strength andadhesion properties of the copolymers. Historically, in order to producea copolymer with sufficient strength, one had to limit the ethylenecontent of the copolymer. It has been observed that there is acorrelation between the ethylene contents of a copolymer and itssoftening point and needle penetration, which is an indication of thecopolymer's strength. Usually, the ethylene content can have a negativecorrelation with the softening point of the copolymer and a positivecorrelation with the needle penetration of the copolymer. In otherwords, the more ethylene that is present in a copolymer, the lower thesoftening point and higher the needle penetration of the copolymer.Thus, increasing the ethylene content in a propylene-ethylene copolymermay decrease the copolymer's softening point, but can also compromiseits strength as shown by an increased needle penetration.

Unlike conventional propylene-ethylene copolymers available today, theinventive copolymers can exhibit a desirable softening point and needlepenetration with relatively high ethylene contents. As previously noted,it can be desirable to utilize ethylene as a comonomer in propylenecopolymers due to the high availability and low costs of ethylenecompared to other alpha-olefins. Furthermore, there can bepolymerization advantages in using ethylene as a comonomer sinceethylene can be much more reactive than many other alpha-olefins.

According to various embodiments, the propylene-ethylene copolymersdescribed herein can comprise varying amounts of ethylene. For example,the propylene-ethylene copolymers can comprise at least 1, 3, 5, 7, 10,12, 14, 15, 17, 18, or 20 and/or not more than 70, 65, 60, 55, 50, 45,40, 35, 30, 27, or 25 weight percent of ethylene. Moreover, thepropylene-ethylene copolymers can comprise in the range of 1 to 70, 3 to65, 5 to 60, 7 to 55, 10 to 50, 12 to 45, 14 to 40, 15 to 35, 17 to 30,18 to 27, or 20 to 25 weight percent of ethylene.

Furthermore, in various embodiments, the propylene-ethylene copolymerscan contain varying amounts of propylene. For example, thepropylene-ethylene copolymers can comprise at least 40, 50, 60, 65, or70 and/or not more than 99, 95, 90, 85, or 80 weight percent ofpropylene. Moreover, the propylene-ethylene copolymers can comprise inthe range of 40 to 99, 50 to 95, 60 to 90, 65 to 85, or 70 to 80 weightpercent of propylene.

In various embodiments, the copolymers can comprise at least 50, 65, 75,or 85 and/or not more than 99, 97.5, 95, or 90 weight percent ofethylene and propylene in combination. Moreover, the copolymers cancomprise in the range of 50 to 99, 65 to 97.5, 75 to 95, or 85 to 90weight percent ethylene and propylene in combination. Additionally oralternatively, the copolymers can comprise a weight ratio of propyleneto ethylene of at least 0.5:1, 1:1, 2:1, or 2.5:1 and/or not more than20:1, 15:1, 10:1, or 5:1. Moreover, the copolymers can comprise a weightratio of propylene to ethylene in the range of 0.5:1 to 20:1, 1:1 to15:1, 2:1 to 10:1, or 2.5:1 to 5:1.

In various embodiments, the copolymers can contain one or more C₄-C₁₀alpha-olefins. As previously noted, C₄-C₁₀ alpha-olefins can be used toincrease the resulting bond strength of the copolymers when utilized inadhesives. These C₄-C₁₀ alpha-olefins can include, for example,1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,and combinations thereof. According to one or more embodiments, thecopolymers can comprise at least 0.5, 1, 2, 3, 4, or 5 and/or not morethan 40, 30, 25, 20, 15, or 10 weight percent of at least one C₄-C₁₀alpha-olefin. Moreover, the copolymers can comprise in the range of 0.5to 40, 1 to 30, 2 to 25, 3 to 20, 4 to 15, or 5 to 10 weight percent ofat least one C₄-C₁₀ alpha-olefin.

As noted above, a lower softening point for the copolymers can bedesirable so that the copolymers can be utilized and processed at lowerapplication temperatures. In various embodiments, the copolymers canhave a softening point of at least 85, 90, 95, 96, 97, 98, 99, 100, 101,102, 103, 104, 105, 106, 107, 108, 109, 110, 113, 115, 116, 119, 120,121, 124, 125, or 127° C. Additionally or alternatively, the copolymerscan have a softening point of not more than 145, 140, 138, 137, 136,135, 134, 132, 130, 129, 128, 127, 126, 125, 124, 123, 122, 121, 120,118, 117, 115, 110, or 109.9° C. as measured according to ASTM E28Standard Test Method for Softening Point of Resins Derived from PineChemicals and Hydrocarbons, by Ring-and Ball Apparatus using a heatingrate of 5° C. per minute and a bath liquid of USP Glycerin.

Moreover, the copolymers can have a softening point in the range of 85to 145° C., 90 to 140° C., 90 to 110° C., 90 to 121° C., 90 to 115° C.,95 to 138° C., 95 to 110° C., 96 to 136° C., 97 to 135° C., 98 to 134°C., 99 to 132° C., 100 to 130° C., 101 to 129° C., 102 to 128° C., 103to 127° C., 104 to 126° C., 105 to 125° C., 106 to 124° C., 107 to 123°C., 108 to 122° C., 109 to 121° C., or 110 to 120° C. as measuredaccording to ASTM E28 as discussed previously.

Despite exhibiting the low softening points described above, thecopolymers can also exhibit desirable needle penetration values.Generally, the lower the needle penetration value, the higher thestrength characteristics and modulus of the copolymer; however, if theneedle penetration gets too low, then adhesive properties can beadversely impacted. In various embodiment, when the softening point isin the range of 90 to 140° C., the needle penetration values of thecopolymers described herein can be defined by the following formula:

y≦−0.000000262249x6+0.000172031278x5−0.046669720165x4+6.701746779438x3−537.286013331959x2+22,802.983472587x−400,204.018086126.

Needle penetration is measured following ASTM D5 Standard Test Methodfor Penetration of Bituminous Materials and utilizing the followingspecifications:

-   -   The weight of the spindle is 47.5+/−0.05 g. The weight of the        ferrule needle assembly is 2.50+/−0.05 g. The total weight of        the needle and spindle assembly is 50.0+/−0.05 g. A weight of        50+/−0.05 g shall also be provided for total load of 100 g.    -   Samples are conditioned in a water bath at temperature of        25+/−0.1° C. [77+/−0.2° F.]    -   The time the needle penetrates into the sample is 5+/−0.1 s.

In various other embodiments, when the softening point is in the rangeof 110 to 140° C., the needle penetration values of the copolymersdescribed herein can be defined by the following formula:

y≦−0.000751414552642x ⁴+0.374053308337937x ³−69.5967657676062x²+5,734.02599677759x−176,398.494888882.

In the above formula, “y” defines the needle penetration (dmm) of thecopolymer and “x” is the softening point (° C.) of the copolymer.

In various embodiments, the copolymers can have a needle penetration ofat least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 15, 20, 30, or 35decimillimeters (“dmm”) as measured according to ASTM D5 as discussedpreviously. Additionally or alternatively, the copolymers can have aneedle penetration of not more than 75, 73.8, 70, 60, 50, 45, 40, 30,29, 28, 27, 26, 25, 24, 23, 22, 21, 20, or 15 dmm as measured accordingto ASTM D5 as discussed previously. Moreover, the copolymers can have aneedle penetration in the range of 1 to 75, 2 to 50, 3 to 30, 4 to 29, 5to 28, 6 to 27, 7 to 26, 8 to 25, 9 to 24, 10 to 23, 11 to 22, 12 to 21,or 13 to 20 dmm as measured according to ASTM D5 as discussedpreviously.

Depending on their intended end use, the copolymers can have varyingsoftening points and needle penetration ranges. In various embodiments,the copolymers can have a softening point in the range of 90 to 121° C.and needle penetration less than 35 dmm. In other embodiments, thecopolymers can have a softening point in the range of 90 to 115° C. anda needle penetration of less than 53 dmm. In various embodiments, thecopolymers can have a softening point in the range of 110 to 138° C. andneedle penetration in the range of 1 to 15 dmm. Furthermore, in certainembodiments, the copolymers can have a softening point in the range of110 to 135° C. and needle penetration in the range of 5 to 15 dmm.Moreover, in certain embodiments, the copolymers can have a softeningpoint in the range of 110 to 130° C. and needle penetration in the rangeof 10 to 15 dmm.

In various embodiments, the copolymers can have a softening point in therange of 110 to 137° C. and needle penetration in the range of 1 to 22dmm. Furthermore, in certain embodiments, the copolymers can have asoftening point in the range of 110 to 135° C. and needle penetration inthe range of 5 to 22 dmm. In other embodiments, the copolymers can havea softening point in the range of 110 to 135° C. and needle penetrationin the range of 10 to 24 dmm. Moreover, in certain embodiments, thecopolymers can have a softening point in the range of 110 to 130° C. andneedle penetration in the range of 10 to 20 dmm.

In various embodiments, the copolymers can have a softening point in therange of 110 to 134° C. and needle penetration in the range of 1 to 25dmm. Furthermore, in certain embodiments, the copolymers can have asoftening point in the range of 110 to 132° C. and needle penetration inthe range of 5 to 25 dmm. Moreover, in certain embodiments, thecopolymers can have a softening point in the range of 110 to 130° C. andneedle penetration in the range of 10 to 25 dmm.

In various embodiments, the copolymers can have a softening point in therange of 110 to 124° C. and needle penetration in the range of 1 to 30dmm. Furthermore, in certain embodiments, the copolymers can have asoftening point in the range of 110 to 122° C. and needle penetration inthe range of 5 to 30 dmm. Moreover, in certain embodiments, thecopolymers can have a softening point in the range of 110 to 120° C. andneedle penetration in the range of 10 to 30 dmm.

In various embodiments, the copolymers can have a softening point in therange of 110 to 120° C. and needle penetration in the range of 30 to 50dmm. Furthermore, in certain embodiments, the copolymers can have asoftening point in the range of 110 to 120° C. and needle penetration inthe range of 35 to 50 dmm. Moreover, in certain embodiments, thecopolymers can have a softening point in the range of 110 to 120° C. andneedle penetration in the range of 30 to 45 dmm.

In various embodiments, the copolymers can have a softening point in therange of 90 to 125° C. and needle penetration of less than 30 dmm.Furthermore, in certain embodiments, the copolymers can have a softeningpoint in the range of 90 to 123° C. and needle penetration of less than35 dmm. Moreover, in certain embodiments, the copolymers can have asoftening point in the range of 90 to 125° C. and needle penetration inthe range of 10 to 30 dmm. In various embodiments, the copolymers canhave a softening point in the range of 90 to 109.9° C. and needlepenetration of less than 73.8 dmm. Furthermore, in certain embodiments,the copolymers can have a softening point in the range of 127 to 140° C.and needle penetration of less than 25 dmm. Moreover, in certainembodiments, the copolymers can have a softening point in the range of124 to 126° C. and needle penetration of less than 30 dmm.

In various embodiments, the copolymers can have a softening point in therange of 121 to 123° C. and needle penetration of less than 40 dmm.Furthermore, in certain embodiments, the copolymers can have a softeningpoint in the range of 119 to 120° C. and needle penetration of less than50 dmm. Moreover, in certain embodiments, the copolymers can have asoftening point in the range of 116 to 118° C. and needle penetration ofless than 60 dmm. In other embodiments, the copolymers can have asoftening point in the range of 113 to 117° C. and needle penetration ofless than 70 dmm.

Generally, lower softening points in the copolymers can sometimes beaccompanied by lower glass transition (“Tg”) temperatures. In variousembodiments, the copolymers can have a glass transition temperature ofat least −100, −80, −60, or −40 and/or not more than about 20, 0, −10,or −20° C. as measured according to DMA. Moreover, the copolymers canhave a Tg in the range of −100 to 20° C., −80 to 0° C., −60 to −10° C.,or −40 to −20° C. as measured according to DMA.

Furthermore, in various embodiments, the copolymers can have a meltviscosity at 190° C. of at least 100, 500, 1,000, 3,000, or 5,000 and/ornot more than about 100,000, 75,000, 50,000, 35,000, or 25,000 cP asmeasured according to ASTM D3236. Moreover, the copolymers can have amelt viscosity at 190° C. in the range of 100 to 100,000, 500 to 75,000,1,000 to 50,000, 3,000 to 35,000, or 5,000 to 25,000 cP as measuredaccording to ASTM D3236.

According to one or more embodiments, the copolymers can have aBrookfield viscosity at 190° C. of at least 100, 300, 500, or 750 and/ornot more than 30,000, 10,000, 5,000, or 2,500 cps as measured accordingto ASTM D3236. Moreover, the copolymers can have a Brookfield viscosityat 190° C. in the range of 100 to 30,000, 300 to 10,000, 500 to 5,000,or 750 to 2,500 cps.

In one or more embodiments, the copolymers described herein can alsohave a number average molecular weight (M_(n)) of less than 100,000,50,000, or 25,000 as determined by gel permeation chromatography.

In various embodiments, the copolymers described herein do not exhibitsubstantial changes in color when subjected to storage conditions atelevated temperatures over extended periods of time. Before any agingdue to storage occurs, the inventive copolymers can have an initialGardner color of less than 4, 3, 2, or 1 as measured according to ASTMD1544. After being heat aged at 177° C. for at least 96 hours, theinventive copolymers can exhibit a final Gardner color of less than 7,5, 3, or 2 as measured according to ASTM D1544. Thus, the inventivecopolymers can retain a desirable color even after prolonged storage andexposure.

Additionally, the copolymers described herein can be amorphous orsemi-crystalline. As used herein, “amorphous” means that the copolymershave a crystallinity of less than 5 percent as measured usingDifferential Scanning calorimetry (“DSC”) according to ASTM E 794-85. Asused herein, “semi-crystalline” means that the copolymers have acrystallinity in the range of 5 to 40 percent as measured using DSCaccording to ASTM E 794-85. In various embodiments, the copolymers canhave a crystallinity of not more than 60, 40, 30, 20, 10, 5, 4, 3, 2, or1 percent as measured using DSC according to ASTM E 794-85.

The Processes for Producing the Propylene-Ethylene Copolymers

In various embodiments, the copolymers can be produced by reactingpropylene monomers and ethylene monomers in the presence of a catalystsystem comprising at least one electron donor.

In various embodiments, the catalyst system can comprise a Ziegler-Nattacatalyst. According to one or more embodiments, the Ziegler-Nattacatalyst can contain a titanium-containing component, an aluminumcomponent, and an electron donor. In certain embodiments, the catalystcomprises titanium chloride on a magnesium chloride support.

The catalyst systems, in certain embodiments, can comprise aheterogeneous-supported catalyst system formed from titanium compoundsin combination with organoaluminum co-catalysts. In various embodiments,the co-catalyst can comprise an alkyl aluminum co-catalyst (“TEAL”).

In one or more embodiments, the catalyst system can have an aluminum totitanium molar ratio of at least 1:1, 5:1, 10:1, or 15:1 and/or not morethan 100:1, 50:1, 35:1, or 25:1. Moreover, the catalyst system can havean aluminum to titanium molar ratio in the range of 1:1 to 100:1, 5:1 to50:1, 10:1 to 35:1, or 15:1 to 25:1. Additionally or alternatively, invarious embodiments, the catalyst system can have a molar ratio ofaluminum to silicon of at least 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, or 6:1and/or not more than 100:1, 50:1, 35:1, 20:1, 15:1, 10:1, or 8:1.Moreover, the catalyst system can have a molar ratio of aluminum tosilicon in the range of 0.5:1 to 100:1, 1:1 to 50:1, 2:1 to 35:1, 2:1 to20:1, 2:1 to 15:1, 2:1 to 10:1, or 2:1 to 8:1.

Electron donors are capable of increasing the copolymer'sstereospecificity. However, it can be important to closely regulate thecontents of the electron donors since they can suppress catalystactivity to unacceptable levels in some circumstances. The electrondonors used during the polymerization process can include, for example,organic esters, ethers, alcohols, amines, ketones, phenols, phosphines,and/or organosilanes. Furthermore, the catalyst system can compriseinternal donors and/or external donors.

In various embodiments, the catalyst system comprises at least oneexternal electron donor. In one or more embodiments, the externalelectron donor comprises at least one alkoxy silane. In particular, incertain embodiments, the alkoxy silane can comprisedicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, or acombination thereof. Moreover, in some embodiments, the alkoxy silanecan comprise, consist essentially of, or consist entirely ofdicyclopentyldimethoxysilane.

It has been observed that the addition of the above external donors tothe catalyst system can increase the hardness (i.e., decrease the needlepenetration) and viscosities of the copolymers. However, contrary towhat has been previously observed in the art, the electron donorsdescribed above can actually lower the softening points of the producedcopolymers instead of increasing it. Furthermore, it has been observedthat substantially all (i.e., greater than 95 percent) of the ethyleneadded to the reactor during the polymerization process can react whenthe above electron donors are used. Thus, this can result in copolymershaving higher ethylene contents and lower propylene contents.Consequently, when using the above electron donors, propylene-ethylenecopolymers can be produced that have higher ethylene contents, but stillexhibit desired balances between softening point and hardness.

In addition, according to various embodiments, the catalyst system canhave a molar ratio of electron donor to titanium of at least 0.1:1,0.5:1, 1:1, 1.25:1, 1.5:1, or 2:1 and/or not more than 20:1, 15:1, 10:1,5:1, 4.5:1, or 4:1. Moreover, the catalyst system can have a molar ratioof electron donor to titanium in the range of 0.1:1 to 20:1, 0.5:1 to15:1, 1:1 to 10:1, 1.25:1 to 5:1, 1.5:1 to 4.5:1, or 2:1 to 4:1.Additionally or alternatively, in various embodiments, the catalystsystem can comprise a molar ratio of TEAL co-catalyst to the electrondonor of at least 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, or 6:1 and/or not morethan 100:1, 50:1, 35:1, 20:1, 15:1, 10:1, or 8:1. Moreover, the catalystsystem can comprise a molar ratio of TEAL co-catalyst to the electrondonor in the range of 0.5:1 to 100:1, 1:1 to 50:1, 2:1 to 35:1, 2:1 to20:1, 2:1 to 15:1, 2:1 to 10:1, or 2:1 to 8:1. In certain embodiments,the type of electron donor can influence the necessary TEAL/electrondonor ratio. For instance, in embodiments where the electron donor isdicyclopentyldimethoxysilane, the TEAL/electron donor ratio can be lessthan 20:1.

The catalyst system can exhibit a catalyst activity in the range of 200to 2,000, 400 to 1,200, or 500 to 1,000 g/g. Catalyst activity iscalculated by measuring the ratio of the weight the polymer made in thereactor to the weight of the catalyst charged into the reactor. Thesemeasurements are based on a reaction time of one hour.

Since the addition of external donors can increase viscosity andmolecular weight, the addition of hydrogen can be required to act as achain terminator during polymerization. For example, the process can becarried out at a hydrogen pressure in the range of 5 to 100, 10 to 80,or 15 to 50 psig.

In various embodiments, the polymerization reaction can occur at atemperature in the range of 100 to 200, 110 to 180, or 120 to 150° C.Furthermore, the polymerization reaction can be carried out a pressurein the range of 500 to 2,000, 700 to 1,500, or 800 to 1,250 psig.

In certain embodiments, the reactor can comprise a stirred reactor andthe polymerization reaction can have a residence time in the reactor inthe range of 0.1 to 6, 0.5 to 4, or 1 to 2 hours. In variousembodiments, the ethylene can be added to the reactor as a gas and thepropylene can be added as a liquid.

End Products Incorporating the Propylene-Ethylene Copolymers

The copolymers described herein can be utilized in a wide array ofapplications including, for example, adhesives, sealants, roofingmembranes, waterproof membranes and underlayments, carpet, laminatedarticles, tapes (e.g. tamper evident tapes, water activated tapes,gummed tape, sealing tape, scrim reinforced tape, veneer tape,reinforced and non-reinforced gummed paper tape, box makers tape, papertape, packaging tape, duct tape, masking tape, invisible tape,electrical tape, gaffer tape, hockey tape, medical tape, etc.), labels(e.g. general purpose label, beverage label, freezer label, smart label,consumer electronics etc.), mastics, polymer blends, wire coatings,molded articles, and rubber additives. In certain embodiments, thecopolymers described herein can be utilized in adhesives, such as, forexample, hotmelt adhesives, water based adhesives, solvent basedadhesives, hot melt pressure-sensitive adhesives, solvent-basedpressure-sensitive adhesives, hot melt nonwoven/hygiene adhesives, andhot melt packaging adhesives. In particular, due to their uniquecombination of softening point and needle penetration as previouslydescribed, adhesives produced from the inventive copolymers can beutilized in a vast array of end products, including hygienic packagingand other packaging applications. In many embodiments, the variousproperties of the inventive copolymers, such as softening point andneedle penetration, can be selected to suit the intended end use of thecomposition incorporating the copolymers.

Furthermore, in various embodiments, the inventive copolymers describedherein can also be used to modify existing polymer blends that aretypically utilized in plastics, elastomeric applications, roofingapplications, cable filling, and tire modifications. The inventivecopolymers can improve the adhesion, processability, stability,viscoelasticity, thermal properties, and mechanical properties of thesepolymer blends.

In various embodiments, the inventive copolymers can be modified toproduce graft copolymers. In such embodiments, the inventive copolymerscan be grafted with maleic anhydride, fumarate and maleate esters,methacrylate esters (e.g., glycidyl methacrylate and hydroxethylmethacrylate), methacrylic acid, vinyl derivatives, silane derivatives,or combinations thereof. These graft copolymers can be produced usingany conventional process known in the art including, for example,transesterification and free radical induced coupling.

The various end uses and end products noted above can utilize theinventive copolymer by itself or can combine it with other additives andpolymers. Suitable polymers that can be combined with the inventivecopolymers to form a polymer blend may include, for example,isoprene-based block copolymers; butadiene-based block copolymers;hydrogenated block copolymers; ethylene vinyl acetate copolymers;polyester; polyester-based copolymers; neoprene; urethane; polyacrylate;acrylate copolymers such as ethylene acrylic acid copolymer, ethylenen-butyl acrylate copolymer, and ethylene methyl acrylate copolymer;polyether ether ketone; polyamide; styrenic block copolymers;hydrogenated styrenic block copolymers; random styrenic copolymers;ethylene-propylene rubber; ethylene vinyl acetate copolymer; butylrubber; styrene butadiene rubber; butadiene acrylonitrile rubber;natural rubber; polyisoprene; polyisobutylene; polyvinyl acetate;polyethylene; polypropylene including atactic polypropylene; aterpolymer formed from the ethylene, propylene, and a diene (EPDM);metallocene-catalyzed polypropylene polymers; ethylene-butenecopolymers; ethylene-hexene copolymers; ethylene-octene copolymers;ethylene-dodecene copolymers; propylene-butene copolymers;propylene-hexene copolymers; propylene-octene copolymers; andpropylene-dodecene copolymers.

In various embodiments, the copolymers described herein can be used toproduce a hot melt adhesive. According to one or more embodiments, theadhesives can comprise at least 1, 5, 10, 20, 30, or 40 and/or not morethan 95, 90, 80, 70, 60, or 55 weight percent of the inventivecopolymer. Moreover, the adhesives can comprise in the range of 1 to 95,5 to 90, 10 to 80, 20 to 70, 30 to 60, or 40 to 55 weight percent of theinventive copolymers. In certain embodiments, the adhesive can beentirely comprised of the inventive copolymer.

Furthermore, depending on the intended end use, these hot melt adhesivescan also comprise various additives including, for example, polymers,tackifiers, processing oils, waxes, antioxidants, plasticizers,pigments, and fillers.

In various embodiments, the adhesives can comprise at least 10, 20, 30,or 40 and/or not more than 90, 80, 70, or 55 weight percent of at leastone polymer that is different from the inventive copolymers. Moreover,the adhesives can comprise in the range of 10 to 90, 20 to 80, 30 to 70,or 40 to 55 weight percent of at least one polymer that is differentfrom the inventive copolymers. These polymers can include any of thepolymers listed above.

In various embodiments, the adhesives can comprise at least 10, 20, 30,or 40 and/or not more than 90, 80, 70, or 55 weight percent of at leastone tackifier. Moreover, the adhesives can comprise in the range of 10to 90, 20 to 80, 30 to 70, or 40 to 55 weight percent of at least onetackifer. Suitable tackifiers can include, for example, cycloaliphatichydrocarbon resins, C₅ hydrocarbon resins; C₅/C₉ hydrocarbon resins;aromatically-modified C₅ resins; C₉ hydrocarbon resins; pure monomerresins such as copolymers or styrene with alpha-methyl styrene, vinyltoluene, para-methyl styrene, indene, methyl indene, C₅ resins, and C₉resins; terpene resins; terpene phenolic resins; terpene styrene resins;rosin esters; modified rosin esters; liquid resins of fully or partiallyhydrogenated rosins; fully or partially hydrogenated rosin esters; fullyor partially hydrogenated modified rosin resins; fully or partiallyhydrogenated rosin alcohols; fully or partially hydrogenated C₅ resins;fully or partially hydrogenated C₅/C₉ resins; fully or partiallyhydrogenated aromatically-modified C₅ resins; fully or partiallyhydrogenated C₉ resins; fully or partially hydrogenated pure monomerresins; fully or partially hydrogenated C₅/cycloaliphatic resins; fullyor partially hydrogenated C₅/cycloaliphatic/styrene/C₉ resins; fully orpartially hydrogenated cycloaliphatic resins; and combinations thereof.Exemplary commercial hydrocarbon resins include Regalite™ hydrocarbonresins (Eastman Chemical).

In various embodiments, the adhesives can comprise at least 1, 2, 5, 8,or 10 and/or not more than 40, 30, 25, or 20 weight percent of at leastone processing oil. Moreover, the adhesives can comprise in the range of2 to 40, 5 to 30, 8 to 25, or 10 to 20 weight percent of at least oneprocessing oil. Processing oils can include, for example, mineral oils,naphthenic oils, paraffinic oils, aromatic oils, castor oils, rape seedoil, triglyceride oils, or combinations thereof. As one skilled in theart would appreciate, processing oils may also include extender oils,which are commonly used in adhesives. The use of oils in the adhesivesmay be desirable if the adhesive is to be used as a pressure-sensitiveadhesive to produce tapes or labels or as an adhesive to adhere nonwovenarticles. In certain embodiments, the adhesive may not comprise anyprocessing oils.

In various embodiments, the adhesives can comprise at least 1, 2, 5, 8,or 10 and/or not more than 40, 30, 25, or 20 weight percent of at leastone wax. Moreover, the adhesives can comprise in the range of 1 to 40, 5to 30, 8 to 25, or 10 to 20 weight percent of at least one wax. Suitablewaxes can include, for example, microcrystalline wax, paraffin wax,waxes produced by Fischer-Tropsch processes, functionalized waxes(maleated, fumerated, or wax with functional groups etc.) and vegetablewax. The use of waxes in the adhesives may be desirable if the adhesiveis to be used as a hot melt packaging adhesive. In certain embodiments,the adhesive may not comprise a wax.

In various embodiments, the adhesives can comprise at least 0.1, 0.5, 1,2, or 3 and/or not more than 20, 10, 8, or 5 weight percent of at leastone antioxidant. Moreover, the adhesives can comprise in the range of0.1 to 20, 1 to 10, 2 to 8, or 3 to 5 weight percent of at least oneantioxidant.

In various embodiments, the adhesives can comprise at least 0.5, 1, 2,or 3 and/or not more than 20, 10, 8, or 5 weight percent of at least oneplasticizer. Moreover, the adhesives can comprise in the range of 0.5 to20, 1 to 10, 2 to 8, or 3 to 5 weight percent of at least oneplasticizer. Suitable plasticizers can include, for example, dibutylphthalate, dioctyl phthalate, chlorinated paraffins, and phthalate-freeplasticizers. Commercial plasticizers can include, for example,Benzoflex™ plasticizers (Eastman Chemical) and Eastman 168™ (EastmanChemical).

In various embodiments, the adhesives can comprise at least 10, 20, 30,or 40 and/or not more than 90, 80, 70, or 55 weight percent of at leastone filler. Moreover, the adhesives can comprise in the range of 1 to90, 20 to 80, 30 to 70, or 40 to 55 weight percent of at least onefiller. Suitable fillers can include, for example, carbon black, calciumcarbonate, titanium oxide, zinc oxide, or combinations thereof.

The adhesive compositions can be produced using conventional techniquesand equipment. For example, the components of the adhesive compositionmay be blended in a mixer such as a sigma blade mixer, a plasticorder, abrabender mixer, a twin screw extruder, or an in-can blend (pint-cans).In various embodiments, the adhesive may be shaped into a desired form,such as a tape or sheet, by an appropriate technique including, forexample, extrusion, compression molding, calendaring or roll coatingtechniques (e.g., gravure, reverse roll, etc.), curtain coating,slot-die coating, or spray coating.

Furthermore, the adhesive may be applied to a substrate by solventcasting processes or by melting the adhesive and then using conventionalhot melt adhesive application equipment known in the art. Suitablesubstrates can include, for example, nonwoven, textile fabric, paper,glass, plastic, films (Polyethylene, Polypropylene, Polyester etc.), andmetal. Generally, about 0.1 to 100 g/m² of the adhesive composition canbe applied to a substrate.

According to one or more embodiments, the hot melt adhesives can have aBrookfield viscosity at 177° C. of at least 100, 300, 500, or 750 and/ornot more than 30,000, 10,000, 5,000, or 2,500 cps as measured accordingto ASTM D3236. Moreover, the hot melt adhesives can have a Brookfieldviscosity at 177° C. in the range of 100 to 30,000, 300 to 10,000, 500to 5,000, or 750 to 2,500 cps. Additionally or alternatively, the hotmelt adhesives can have a loop tack of 0.1, 0.5, 1, or 1.5 and/or notmore than 20, 15, 10, or 5 lbf as measured according to ASTM D6195.Moreover, the hot melt adhesives can have a loop tack in the range of0.1 to 20, 0.5 to 15, 1 to 10, or 1.5 to 5 lbf as measured according toASTM D6195.

Furthermore, in various embodiments, the hot melt adhesives can have apeel strength of at least 1, 2, 5, 10, or 15 and/or not more than 50,40, 35, 30, or 25 g/mm as measured according to ASTM D903. Moreover, thehot melt adhesives can have a peel strength in the range of 1 to 50, 2to 40, 5 to 35, 10 to 30, or 15 to 25 g/mm as measured according to ASTMD903. Additionally or alternatively, the hot melt adhesives can have a90° peel strength of at least 0.05, 0.1, 0.2, or 0.5 and/or not morethan 20, 10, 5, or 1 lbf/inch as measured according to ASTM D903.Moreover, the hot melt adhesives can have a 90° peel strength in therange of 0.05 to 20, 0.1 to 10, 0.2 to 5, or 0.5 to 1 lbf/inch asmeasured according to ASTM D903.

According to various embodiments, the adhesives containing the inventivecopolymers can have a broad operating window and may have an applicationwindow from 80 to 230° C. This broad operating window can bedemonstrated by the peel strengths of the adhesives at differenttemperatures. Add-on level can be from 0.5-30 gsm. In one or moreembodiments, the hot melt adhesives can have a peel strength for samplesapplied at lower temperature (such as 100-145° C.) of at least 2, 5, 25,or 40 and/or not more than 250, 200, or 175 g/mm as measured accordingto ASTM D903. Moreover, the hot melt adhesives can have a peel strengthfor samples applied at lower temperature (such as 100-145° C.) in therange of 2 to 250, 25 to 200, or 40 to 175 g/mm as measured according toASTM D903. Additionally or alternatively, the hot melt adhesives canhave a peel strength at for samples applied at higher temperature (suchas 145-180° C.)—of at least 1, 5, 30, or 40 and/or not more than 250,200, or 150 g/mm as measured according to ASTM D903. Moreover, the hotmelt adhesives can have a peel strength for samples applied at highertemperature (such as 145-180° C.) in the range of 1 to 250, 30 to 200,or 40 to 150 g/mm as measured according to ASTM D903.

According to one or more embodiments, the hot melt adhesives can have aprobe tack of at least 0.1, 0.2, or 0.3 and/or not more than 5, 3, 2, or1 kg as measured according to ASTM D9279. Moreover, the hot meltadhesives can have a probe tack in the range of 0.1 to 3, 0.2 to 2, or0.3 to 5 kg as measured according to ASTM D9279. Furthermore, in variousembodiments, the hot melt adhesives can have a holding power of at least0.1, 0.5, or 1 and/or not more than 50000, 10000, 5000, 1000, 500, 100,50, 20, 10, 7, or 4 hours as measured according to ASTM D3654. Moreover,the hot melt adhesives can have a holding power in the range of 0.1 to10, 0.5 to 7, or 1 to 4 hours as measured according to ASTM D3654.

According to various embodiments, the hot melt adhesives can have a peeladhesion failure temperature (“PAFT”) of at least 2, 10, 25, or 45and/or not more than 200, 120, or 80° C. as measured according to ASTMD4498. Moreover, the hot melt adhesives can have a PAFT in the range of2, 10 to 200, 25 to 120, or 45 to 80° C. as measured according to ASTMD4498. Additionally or alternatively, the hot melt adhesives can have ashear adhesion failure temperature (“SAFT”) of at least 2, 5, 10, 25,50, or 75 and/or not more than 200, 150, or 125° C. as measuredaccording to ASTM D4498. Moreover, the hot melt adhesives can have aSAFT in the range of 2 to 200, 50 to 150, or 75 to 125° C. as measuredaccording to ASTM D4498.

In various embodiments, the adhesives containing the inventivecopolymers do not exhibit substantial changes in color when subjected tostorage conditions at elevated temperatures over extended periods oftime. Before any aging due to storage occurs, the adhesives can have aninitial Gardner color of less than 18, 15, 10, 8, 5, 4, 3, 2, or 1 asmeasured according to ASTM D1544. After being heat aged at 177° C. forat least 96 hours, the adhesives can exhibit a final Gardner color ofless than 18, 15, 10, 7, 5, 3, 2 or 1 as measured according to ASTMD1544. Thus, the adhesives can retain a desirable color even afterprolonged storage and exposure.

This invention can be further illustrated by the following examples ofembodiments thereof, although it will be understood that these examplesare included merely for the purposes of illustration and are notintended to limit the scope of the invention unless otherwisespecifically indicated.

EXAMPLES Example 1

In this example, various propylene-ethylene copolymers were produced ina two-liter stirred reactor with an average residence time of about onehour. The reactor temperature was maintained at approximately 140° C.and a pressure of 900 psig. The propylene was fed into the reactor as aliquid, while the ethylene was fed into the reactor as a gas. Thepolymerization occurred in the presence of a Ziegler-Natta catalyst,which was a titanium chloride on a magnesium chloride support. Thisparticular catalyst is a heterogeneous-supported catalyst system formedfrom titanium compounds in combination with alkyl aluminum co-catalyst(“TEAL”). The catalyst system contained an Al/Ti mole ratio of 21. Anyunreacted monomer and other vapors were vented from the reactor upondischarge of the copolymer.

Samples 1-11 were produced using the aforementioned catalyst system andan external electron donor. As noted below, the electron donor waseither cyclohexylmethyldimethoxysilane (“C”) ordicyclopentyldimethoxysilane (“D”). Comparative sample 1 (C1) wasproduced using the above catalyst system in the absence of any electrondonors. The amount of added electron donor varied for each sample asindicated by Donor/Ti molar ratio.

The copolymers produced from this reaction are described in TABLE 1below, along with their various properties and the reaction conditionsused to produce them. It should be noted that needle penetration wasmeasured using a penetrometer in accordance with ASTM D5 as discussedpreviously without actually running the specimens in water; however, thespecimens were conditioned in water prior to running the test.

TABLE 1 Copolymer Sample 1A 1B 1C 1D 1E 1F 1G 1H 1I 1J 1K C1 Al/Ti mole21 21 21 21 21 21 21 21 21 21 21 21 ratio Silane Donor C C D D D D D D DD D — Donor/Ti, 0.5 1.2 1.0 2.0 2.0 2.0 2.5 2.5 3.0 2.0 2.0 — mole ratioHydrogen 40 20 15 25 25 40 40 25 50 80 80 — (psig) Reactor 140 140 140140 140 140 140 140 140 140 140 140 Temp, ° C. Reactor 900 900 900 900900 900 900 900 900 900 900 900 Press. (psig) Catalyst 714.3 1003.3920.4 887.8 817.1 728.4 803.1 842.9 780.8 824.3 841.7 — Activity (g/g)Visc. @ 1853 5863 9088 9838 21125 6850 10238 16575 5525 1122 1748 7013190 ° C., cP Softening 130.3 142.2 134.8 131.6 128.6 121.8 126.3 132.6119 117.7 129.1 120.7 Point (° C.) Needle Pen. 20 14 15 29 17 20 22 2128 26 20 82 (dmm) Wt. % 15.2 12.5 17.5 24.6 20.2 22.6 25.3 22.6 25.221.1 19.5 21.7 Ethylene Wt. % 84.8 87.5 82.5 75.4 79.8 77.4 74.7 77.474.8 78.9 80.5 78.3 Propylene Poly Yield (g) 537.5 780.0 709.6 712.9656.1 584.9 657.7 690.3 652.0 661.9 675.9 720.9

As shown above in TABLE 1, the addition of the external donor generallyincreased hardness, which was indicated by a decrease in needlepenetration, along with increasing the softening point and viscosity ofthe copolymers. As depicted in TABLE 1, samples produced with theexternal donor had significantly lower needle penetration values thanthe comparative sample (C1). Furthermore, it was observed that thecomparative sample was very tacky, but still lacked the strength of thesamples represented by needle penetration values below 30 dmm.

Previous studies indicate that external donor levels greater than 1.25:1(donor:Ti molar ratio) start to adversely impact properties of thecopolymers. In contrast to these studies, it was observed in thisexample that polymer properties improved at external donor levels ofgreater than 1.25:1 (donor:Ti molar ratio). Since the addition ofexternal donors can increase viscosity and molecular weight, theaddition of hydrogen, or a higher level of hydrogen, can be required toact as a chain terminator during polymerization compared topolymerization of a similar composition with no external donor added.

FIGS. 1A and 1B depict the viscoelastic characteristics of Samples 1B,1E, and 1F from TABLE 1. Furthermore, FIGS. 1A and 1B also provide theviscoelastic characteristics of various commercially-availablecopolymers to serve as a comparison. These commercially-availablecopolymers include INFUSE™ 9817 (Dow), AFFINITY™ GA1900 (Dow), andEastoflex™ E1060 (Eastman). FIG. 1A depicts the elastic modulus (G′) ofthe copolymers, while FIG. 1B depicts the tan delta of the copolymers.

As shown in FIGS. 1A and 1B, Sample 1B showed a desirable elasticmodulus (G′) plateau from −15 to 100° C., representing the elasticcharacteristics over a wide application temperature range. This isimportant in hot melt pressure sensitive adhesives (“PSA”) applications,such as tapes and labels, because the G′ plateau (i.e., the flatness ofthe curve) typically represents the energy absorption and desorptioncharacteristics, as well as the strength of the adhesive over a measuredtemperature range. After the plateau, the copolymer can start to flow.Previously, the flat nature of G′ for olefinic copolymers was onlyachievable through specialized catalytic processes (metallocenecatalysis) and/or incorporation of alpha-olefins.

Example 2

In this example, various propylene-ethylene copolymers were producedusing the process and system described in Example 1; however, theexternal electron donor used in this example wascyclohexylmethyldimethoxysilane. Furthermore, the amounts of electrondonor added for each sample were varied as indicated by the donor/Timolar ratio. The copolymers produced during this process are describedin TABLE 2 below, along with their various properties and the reactionconditions used to produce them.

TABLE 2 Copolymer Sample 2A 2B 2C 2D 2E 2F 2G Al/Ti mole 21 21 21 21 2121 21 ratio Donor/Ti, 1.1 1.2 0.5 1.0 1.0 1.5 2.0 mole ratio TEAL/Donor,31.3 29.6 70.0 32.9 32.9 24.7 16.5 mole ratio Hydrogen 40 20 20 25 25 2525 (psig) Reactor 140 140 140 140 140 140 140 Temp, ° C. Reactor 900 900900 900 900 900 900 Press. (psig) Catalyst 843.9 1003.3 1006.8 1001.3957.2 962.9 904.1 Activity (g/g) Visc. @ 3600 6600 5175 4865 7263 55384715 190° C., cP Softening 140.3 138.4 145.3 126.6 135.9 133 129.6 Point(° C.) Needle Pen. 10 14 17 32 24 23 32 (dmm) Wt. % 10.0 10.0 10.0 15.013.0 15.0 15.0 Ethylene Flow Wt. % 11.7 11.9 11.3 19.3 17.2 18.2 19.3Ethylene Wt. % 88.3 88.1 88.7 80.7 82.8 81.8 80.7 Propylene Poly Yield(g) 648.7 780.0 760.1 772.0 738.0 757.8 726.0

As depicted in TABLE 2, the use of cyclohexylmethyldimethoxysilane asthe external donor was able to produce copolymers with a desirablecombination of needle penetration and softening point. However, thisbalance was largely affected by the donor/Ti molar ratio. As shown inSamples 2F and 2G in TABLE 2, when the donor/Ti molar ratio wasincreased from 1.5:1 to 2:1, there was a slight decrease in softeningpoint and a significant increase in needle penetration, which was notdesirable.

Example 3

In this example, various propylene-ethylene copolymers were producedusing the process and system described in Example 1. The externalelectron donor used in this example was dicyclopentyldimethoxysilane.Furthermore, the amounts of electron donor added for each sample wasvaried as indicated by the donor/Ti molar ratio. The copolymers producedduring this process are described in TABLE 3 below, along with theirvarious properties and the reaction conditions used to produce them

TABLE 3 Copolymer Sample C1 C2 3A 3B 3C 3D 3E 3F 3G 3H 3I 3J 3K 3L 3MAl/Ti mole 21 21 21 21 21 21 21 21 21 21 21 21 21 21 21 ratio Donor/Ti,0.3 1.5 3.0 3.0 4.0 2.0 2.0 3.0 3.0 3.0 3.0 3.0 3.0 2.0 2.0 mole ratioTEAL/Donor, 71.0 15.8 7.0 7.0 5.2 10.4 10.4 7.0 7.0 7.0 7.0 7.0 7.0 10.410.4 mole ratio Hydrogen 20 25 80 50 50 80 25 50 33 33 30 30 80 80 80(psig) Reactor 140 140 140 140 140 140 140 140 140 140 140 140 140 140140 Temp, ° C. Reactor 900 900 900 900 900 900 900 900 900 900 900 900900 900 900 Press. (psig) Catalyst 862.0 1037.1 723.2 793.4 612.8 880.6808.8 630.1 653.5 648.1 658.6 584.1 750.9 636.9 817.1 Activity (g/g)Visc. @ 7613 4625 1055 3150 5963 1053 16425 6250 86000 93100 19275 168752332 2308 1590 190° C., cP Softening 140.2 143.2 114.1 109.9 97.4 128.2136.4 119.9 132.2 135.6 123.6 118.7 117.6 122.7 128.8 Point (° C.)Needle Pen. 22 27 37 40 63 21 23 21 13 8 19 18 20 15 12 (dmm) Wt. % 10.015.0 15.0 17.5 17.5 13.0 15.0 13.0 13.0 13.0 13.0 13.0 12.0 12.0 12.0Ethylene Flow Wt. % 14.5 17.3 24 25.8 31.1 18.2 21.3 24.2 20.2 20.1 22.424.1 19.9 22.8 18.5 Ethylene Wt. % 85.5 82.7 76 74.2 68.9 81.8 78.7 75.879.8 79.9 77.6 75.9 80.1 77.2 81.5 Propylene Poly Yield (g) 644.0 816.2603.9 662.5 531.3 707.1 649.5 526.1 545.7 541.2 549.9 487.7 627.0 511.4656.1

As shown in TABLE 3, the amount of dicyclopentyldimethoxysilane neededto produce copolymers with the desired softening point and needlepenetration varies from the amount of cyclohexylmethyldimethoxysilaneneeded as shown above in Example 2. As demonstrated by comparativesamples C1 and C2, dicyclopentyldimethoxysilane levels generally neededto be at 2:1 or greater to achieve the desired properties in theproduced copolymers. Moreover, it was observed that copolymers producedusing dicyclopentyldimethoxysilane generally had much lower softeningpoints compared to those produced using cyclohexylmethyldimethoxysilane.Furthermore, the copolymers produced using dicyclopentyldimethoxysilanewere able to maintain desirable needle penetration values.

Comparing Samples 3C and 3F in TABLE 3 shows that increasing thedicyclopentyldimethoxysilane levels from 3:1 to 4:1 (at 17.5% ethyleneflow) results in more ethylene being incorporated into the polymer,thereby yielding a copolymer with a lower softening point.

Another noteworthy result is observed when comparing Samples 3D and 3F,both of which were produced using the same ethylene flow (13%) and hadthe same needle penetration (21 dmm). However, by increasing thedicyclopentyldimethoxysilane levels from 2:1 to 3:1, Sample 3Funexpectedly had an increased ethylene content (24.2%) compared toSample 3D (18.2%). This increased amount of ethylene led to the lowersoftening point in Sample 3F. Furthermore, it is theorized that thepropylene portion of Sample 3F is also more stereoregular (i.e., harder)than that of Sample 3D, thereby offsetting the softness that is usuallyaccompanied with a higher ethylene content.

Example 4

Adhesives were produced with Samples 1B, 1E, and 1F from Example 1. Theadhesives were produced in pint-sized cans using mechanical agitationwith a paddle-type agitator controlled by a variable speed motor with aheat block set at 177° C. The copolymer, along with antioxidant, wereintroduced into the pint-sized can and heated to 177° C. under anitrogen blanket. Resin and oil were then introduced into the mixtureafter the copolymer was melted. In some cases, wax can be also addedalong with resin and/or oil or in place of resin and/or oil. Thismixture was agitated for 30 minutes until it was completely homogenous.After thorough mixing, the adhesive was poured into a silicone-linedcardboard box and allowed to cool. TABLE 4, below, describes thecomposition and properties of these adhesives. In addition, comparativeadhesives were produced using INFUSE™ 9807 block copolymer (Dow) andKraton® D1102 copolymer (Kraton). It should be noted that thecompositional components recited in TABLE 4 are based on weightpercentage.

TABLE 4 Comparative Comparative Inventive Inventive Inventive MaterialsAdhesive 1 Adhesive 2 Adhesive 1 Adhesive 2 Adhesive 3 INFUSE ™ 9807 20Kraton ® D1102 19.7 Copolymer 40 Sample 1B Copolymer 40 Sample 1ECopolymer 40 Sample 1F Regalite ™ S5100 59.7 Regalite ™ R1090 54 48.548.5 48.5 Kaydol Mineral Oil 10.5 10.5 10.5 Calsol 5550 Oil 25 19.6Irganox ® 1010 1 1 1 1 1 Total 100 100 100 100 100 300 mm peel 13.1 14.62.3 21.5 13.3 strength (g/mm) Brookfield Visc. ~1800 ~1400 806 2167 940177° C. (cps)

Viscoelastic characteristics of Comparative Adhesive 1, ComparativeAdhesive 2, Inventive Adhesive 2, and Inventive Adhesive 3 in TABLE 4were analyzed using Dynamic Mechanical Analysis (“DMA”). FIG. 2 depictsthe viscoelastic characteristics of these adhesives. The adhesives inTABLE 4 were also tested as disposable diaper construction adhesives andwere evaluated for adhesive peel strength as measured according to ASTMD903 using Instron after the adhesive had been applied between anonwoven fabric and polyethylene backing using air-assisted spiralspraying equipment (Acumeter Spray Coater).

Based on FIG. 2 and TABLE 4, the inventive adhesives show similarviscoelastic characteristics to adhesives produced fromcommercially-available copolymers. Furthermore, the inventive adhesivesalso exhibited superior strength as indicated by the higher peelstrengths.

Example 5

A pressure sensitive adhesive for labels was produced using the processdescribed in Example 4. The adhesive was produced using Sample 1E fromExample 1. TABLE 5, below, depicts the compositional makeup of thisadhesive.

TABLE 5 Inventive Adhesive Weight % Copolymer Sample 1E 60 Eastotac ™H100W 29.5 Calsol 5550 9.5 Antioxidant 1

The viscoelastic characteristics of this adhesive were measured usingDMA and are depicted in FIG. 3. This adhesive was also evaluated foradhesive peel (90° peel) strength and loop tack using Instron after theadhesive had been directly coated onto vellum using a hot melt knifecoater. The adhesive had a 90° peel strength of 0.6 lbf/inch and a looptack of 1.8 lbf.

Thus, this adhesive can be used as a label adhesive since it exhibitsdesirable viscoelastic characteristics as shown in FIG. 3 and idealadhesive peel and tack properties.

Example 6

Hot melt adhesives for packaging applications were produced using theprocess described in Example 4. All of the adhesives produced for thisexample comprised 39.8 weight percent of the respectivepropylene-ethylene copolymer, 39.8 weight percent of Eastotac™ H-100Whydrocarbon resin, 19.9 weight percent of Sasol H1 wax (Sasol), and 0.6weight percent of antioxidant. It should be noted that some of theseadhesives were formed from copolymers produced and described in theprevious examples (Samples 1F and 2B), which are noted in TABLE 6 below.As for the remaining listed copolymers (Samples 6A-6D), they wereproduced in accordance with the process described in Example 1. TABLE 6,below, provides various properties and characteristics of the producedadhesives. Furthermore, TABLE 6 notes the electron donor used to producethe listed copolymers. These electron donors includedcyclohexylmethyldimethoxysilane (“C”), dicyclopentyldimethoxysilane(“D”), and tetraethoxysilane (“TEOS”). The adhesives were evaluated forvarious adhesive properties, such as peel adhesion failure temperature(“PAFT”) (ASTM D4498), shear adhesion failure temperature (“SAFT”) (ASTMD4498), % fiber tear (ASTM D4498), and open time/set time (ASTM D4497).

TABLE 6 Copolymers in Adhesives Sample Sample Sample Sample SampleSample 1F 2B 6A 6B 6C 6D Properties of Needle Pen. (dmm) 20 14 24 24 505 Copolymers Softening Point (° C.) 121.8 138.4 126.5 135.9 145.6 154.7Electron Donor D C D C TEOS C Wt. % Ethylene 22.6% 11.9% 21.7% 17.2%13.3% 10% Properties of % Fiber Tear (135° F.) 75 75 25 100 25 0 theAdhesives % Fiber Tear 100 0 50 100 100 0 (Room Temp) % Fiber Tear (40°F.) 0 0 0 50 50 0 % Fiber Tear (20° F.) 0 0 0 50 75 0 Open Time/ >30/20 30/10 >30/20 30/10 20/10  32/20 Set Time (sec) SAFT/PAFT (° C.)   98/56115/68   99/51 99/75 99.6/74.6 100/62 Brookfield 6850 6600 6700 72638850 6313 Visc. 177° C. (cps)

It should be noted that the adhesive produced with Sample 6D did nothave any noticeable fiber tear due to its low needle penetration asdepicted in TABLE 6.

The viscoelastic characteristics of the adhesive produced from Sample 1F(labeled as “Inventive Adhesive 5”) are compared in FIG. 4 with anadhesive produced from Affinity™ GA1950 (Dow). This comparative adhesivewas produced based on the same formulation used to produce the adhesivesin TABLE 6. This comparative adhesive is listed in FIG. 6 as“Comparative Adhesive 3.” It should also be noted that this comparativeadhesive had a SAFT of 93.6/3.6° C., a PAFT of 71.8/3.4° C., an opentime/set time of 15/5 seconds, and a Brookfield viscosity at 177° C. of177 cps. As shown in FIG. 4 and TABLE 6, the inventive adhesivesexhibited desirable viscoelastic characteristics and adhesive propertiesthat are comparable to standard adhesives in the industry.

Example 7

Hot melt adhesives for nonwovens were produced using the inventivepropylene-ethylene copolymers and various polymers. Thepropylene-ethylene copolymers used to manufacture these adhesive sampleswere produced in accordance with the process described in Example 1. Thevarious properties and characteristics of the copolymers used to producethe adhesive samples are listed in TABLE 7 below. Furthermore, TABLE 7indicates the electron donor that was used to produce the respectivecopolymer (cyclohexylmethyldimethoxysilane (“C”) ordicyclopentyldimethoxysilane (“D”)).

TABLE 7 Copolymer Sample 7A 7B 7C 7D Visc. @ 190° C., cP 2520 2960 25907363 Softening Point (° C.) 137.5 139.4 134.1 116.1 Needle Pen. (dmm) 1415 14 27 Wt. % Ethylene 11.7 11.9 11.3 19.3 Wt. % Propylene 88.3 88.188.7 80.7 Electron Donor D C C D

The adhesives were produced in accordance with the process described inExample 4. The adhesives were produced with various polymers andadditives including Vistamaxx™ 6202 (ExxonMobil), Infuse™ 9807 (Dow),L-MODU S400 (Idemitsu), Kraton® 1102 (Kraton), Kraton® 1161 (Kraton),Kraton® 1657 (Kraton), Regalite™ R1090 (Eastman Chemical), Kaydolmineral oil (Sonneborn), and Irganox® 1010 (BASF). The Brookfieldviscosity and the peel strength of the produced adhesives were measuredas described above. TABLE 8, below, describes the composition andproperties of these inventive adhesives, which are labeled as “IA.” Itshould be noted that the compositional components recited in TABLE 8 arebased on weight percentage and that all components add up to 100percent; however, this does not include the 1 percent of antioxidant(Irganox® 1010), which was added after all other components werecombined. The weight percentage for the antioxidant was based off thecombined weight percentage of the other components.

TABLE 8 Adhesives IA1 IA2 IA3 IA4 IA5 IA6 IA7 IA8 IA9 Composition Sample7A 70 of Adhesives Sample 7B 70 Sample 7C 70 Sample 7D 20 20 20 20 20 20Vistamaxx ™ 6202 20 Infuse ™ 9807 20 LMODU S400 20 Kraton ® 1102 (SBS)20 Kraton ® 1161 (SIS) 20 Kraton ® 1657 (SEBS) 20 Regalite ™ R1090 30 3030 48.5 48.5 48.5 48.5 48.5 48.5 Kaydol Mineral Oil 10.5 10.5 10.5 10.510.5 10.5 Irganox ® 1010 1 1 1 1 1 1 1 1 1 Brookfield 1675 1775 143014900 7725 1250 3760 7200 10250 Visc. 177° C. (cps) Peel strength 9.86.6 4 21.5 18.6 9.8 6.6 4 21.5 (g/mm)

As shown in TABLE 8, the inventive adhesives exhibited desirableadhesive properties that are comparable to standard adhesives in theindustry.

Example 8

Hot melt adhesives for hygienic applications were produced using theinventive propylene-ethylene copolymers depicted in TABLE 9. Thecopolymers were produced in accordance with the process described inExample 1 using dicyclopentyldimethoxysilane as the electron donor.

TABLE 9 Copolymer Sample 8A 8B 8C Visc. @ 190° C., cP 20000 16000 2200Softening Point (° C.) 135 125 133 Needle Pen. (dmm) 22 17 20 Wt. %Ethylene 22 22 22 Wt. % Propylene 78 78 78

The adhesives were produced in accordance with the process described inExample 4. The adhesives were produced with various additives includingEastotac™ H-100W (Eastman Chemical), Regalite™ R1090 (Eastman Chemical),Kaydol mineral oil (Sonneborn), and Irganox® 1010 (BASF). TABLE 10,below, describes the composition and properties of these inventiveadhesives, which are labeled as “IA.” It should be noted that thecompositional components recited in TABLE 10 are based on weightpercentage.

The coatability, sprayability, and adhesive performance of the inventiveadhesives were compared against adhesives containing acommercially-available styrenic block copolymer (“SBC”) and acommercially-available olefin-based copolymer as shown in TABLE 10. Thecoating/spraying analysis was performed using an Acumeter and Nordson CFnozzle with different add-ons (2, 3, and 4 gsm) at 800, 600, and 400ft/min (6 gsm at 350 ft/min for 3 samples) at two different temperatures(137° C. and 163° C.). The tested substrates were 1 mil polyethylene anda 15 gsm spun bound nonwoven. The sprayability was observed and markedas “good,” “poor,” or “no” (i.e., not sprayable) after observing thespraying of adhesive at the designated temperature. The Brookfieldviscosity, softening point, needle penetration, and the peel strength ofthe produced adhesives were also measured as described above. The widthof the adhesive samples tested for peel strength was 15 to 20 mm.

TABLE 10 Adhesives Com. Com. SBC- Olefin- IA1 IA2 IA3 IA4 IA5 IA6 IA7Based Based Composition of Sample 8A 40 40 40 60 Adhesives Sample 8B 4060 Sample 8C 70 Eastotac ™ 48.5 H-100W Regalite ™ 48.5 48.8 34.5 48.534.5 29 R1090 Mineral Oil 10.5 10.5 10.5 4.5 10.5 4.5 Irganox ® 1 1 1 11 1 1 1010 Brookfield 1688 2133 2760 6425 1515 5300 913 N/A N/A Visc.190° C. (cps) Peel N/A 172 143 136 111 84 49 N/A N/A strength for 137°C. Samples (g) Peel 130 136 122 116 117.7 60 50 101 137 strength for163° C. Samples (g) Sprayability at Good/ Good/ Good/ Good/ Good/ Good/Good/ Poor/ No/ 137° C./163° C. Good  Good  Good  Good  Good  Good Good  Good Poor Softening 120.4 113.3 115.9 125.2 106.7 114.8 123.7 N/AN/A Point (° C.) Needle 55 51 43 32 38 26 28 N/A N/A Penetration (dmm)

It should be noted that peel strength tests of 137° C. samples wereinconclusive for the two comparative commercial adhesives due to thepoor sprayability of these adhesives. As shown in TABLE 10, theinventive adhesives exhibited desirable coatability and sprayability atlow and high temperatures, thereby indicating a broad operating window.Furthermore, the inventive adhesives exhibited adhesive properties thatare either comparable or superior to standard adhesives in the industry.

Example 9

Hot melt adhesives for packaging applications were produced using theinventive propylene-ethylene copolymers depicted in TABLE 11.Furthermore, comparative adhesives were produced from a comparativepropylene homopolymer (“CPH”) as depicted in TABLE 11. The copolymersused to manufacture these adhesive samples were produced in accordancewith the process described in Example 1. Furthermore, TABLE 11 alsoindicates the electron donor that was used to produce the copolymers(cyclohexylmethyldimethoxysilane (“C”) or dicyclopentyldimethoxysilane(“D”)).

TABLE 11 Copolymer Sample CPH 9A 9B Visc. @ 190° C., cP 1028 3165 2520Softening Point (° C.) 135 132.1 137.5 Needle Pen. (dmm) 22 12 14 Wt. %Ethylene 0 9.9 16.7 Wt. % Propylene 100 90.1 83.3 Electron Donor C C D

The adhesives were produced in accordance with the process described inExample 4. The adhesives were produced with various additives includingEastotac™ H-100W (Eastman Chemical), Eastotac™ H-130W (EastmanChemical), Sasol wax H-1 (Sasol), and Irganox® 1010 (BASF). TABLE 12,below, describes the composition and properties of the inventiveadhesives, which are labeled as “IA,” and the comparative adhesives(“CA”). It should be noted that the compositional components recited inTABLE 12 are based on weight percentage. The initial viscosities of theadhesives were measured at 162° C. and 177° C., along with the SAFT,PAFT, and open/set times. The SAFT measurements were performed tounderstand the shear strength of the adhesives over a temperature periodin a SAFT oven. Viscosity profiles of the adhesives were generated todetermine the processability characteristics. Furthermore, the initialGardner color before aging and adhesive clarity at 177° C. were alsomeasured and observed.

TABLE 12 Adhesives CA1 CA2 IA1 IA2 IA3 Composition CPH 39.8 59.8 ofAdhesives Sample 9A 39.8 59.8 Sample 9B 39.8 Eastotac ™ 39.8 H-100WEastotac ™ 39.8 19.8 39.8 19.8 H-130W Sasol wax H-1 19.8 19.8 19.8 19.819.8 Irganox ® 1010 0.6 0.6 0.6 0.6 0.6 Brookfield Visc. 465 750 32509062 575 162° C. (cps) Brookfield Visc. 330 545 2192 6366 417 177° C.(cps) Open/Set time (s) 20/10 N/A 15/10 15/10 N/A PAFT (° C.) 77.4 43.383.6 54.9 63 (4.7) (3.8) (2.6) (9) (2) SAFT (° C.) 108.6 199.6 120.3136.5 101 (5) (2.5) (0.4) (0.4) (2) Gardner Color 2 4 5 6 1 (Initial)Adhesive Clarity clear clear hazy hazy clear (177° C.)

As shown in TABLE 12, the inventive adhesives exhibited adhesiveproperties that are either comparable or superior to adhesives producedfrom propylene. The inventive adhesives can exhibit desirable clarityand color, along with desirable processability as indicated by theirviscosities.

Example 10

Hot melt adhesives for packaging applications were produced using theinventive propylene-ethylene copolymers depicted in TABLE 13.Furthermore, comparative adhesives were produced from Affinity™ GA1950(Dow) and comparative polymers (“CP”) as depicted in TABLE 13. Thecopolymers used to manufacture these adhesive samples were produced inaccordance with the process described in Example 1. Furthermore, TABLE13 also indicates the electron donor that was used to produce thecopolymers.

TABLE 13 Copolymer Sample CP1 CP2 CP3 10A 10B Visc. @ 190° C., cP 83508812 29950 7825 19975 Softening Point (° C.) 157.5 155.8 157.3 111.9107.7 Needle Pen. (dmm) 7 9 1 29 37 Wt. % Ethylene 0 0 6.2 22.8 27.9 Wt.% Propylene 100 100 93.8 97.2 92.1 Electron Donor None None Anisole D D

The adhesives were produced in accordance with the process described inExample 4. The adhesives were produced with various additives includingRegalite™ R1090 (Eastman Chemical), Escorez® 5300 (Exxonmobil),Piccotac™ 1095 (Eastman Chemical), Piccotac™ 7590 (Eastman Chemical),Sasol wax H-1 (Sasol), and Irganox® 1010 (BASF). TABLE 14, below,describes the composition and properties of the inventive adhesives,which are labeled as “IA,” and the comparative adhesives labeled as“CA.” It should be noted that the compositional components recited inTABLE 14 are based on weight percentage and that all components add upto 100 percent; however, this does not include the 1 percent ofantioxidant (Irganox® 1010), which was added after all other componentswere combined. The weight percentage for the antioxidant was based offthe combined weight percentage of the other components.

The initial viscosities of the adhesives were measured at 150° C., 162°C., and 177° C., along with the SAFT, PAFT, and open/set times.Viscosity profiles of the adhesives were generated to determine theprocessability characteristics of the adhesives. The SAFT measurementsare performed to understand the shear strength of the adhesives over atemperature period in a SAFT oven. Furthermore, the adhesive clarity at177° C. was also observed.

TABLE 14 Adhesives CA1 CA2 CA3 CA4 IA1 IA2 CA5 CA6 IA3 CA7 CA8 IA4 IA5CA9 CA10 IA6 IA7 Compo- Affinity 40 sition of GA1950 Adhesives CP1 40CP2 40 40 40 40 CP3 40 40 40 40 10A 40 40 40 40 10B 40 40 40 Regalite ™40 40 40 40 40 40 R1090 Escorez ® 40 40 40 5300 Piccotac ™ 40 40 40 401095 Piccotac ™ 40 40 40 40 7590 Sasol wax 20 20 20 20 20 20 20 20 20 2020 20 20 20 20 20 20 Irganox ® 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1010Visc. 150° C. 1867 7308 3685 30150 675 3360 N/A N/A 4000 N/A 248300 3029607 26550 87000 3604 752 (cps) Visc. 162° C. 1300 810 940 3275 417 24901150 3080 2935 910 2895 1980 432 890 2820 2390 570 (cps) Visc. 177° C.932 607 670 1887 310 1320 860 2370 1872 685 2050 1692 317 815 1900 1507427 (cps) Open/Set 30/40 40/10 — — — — — — — — — — — — — — — time (s)PAFT (° C.) 60.6 72.9 75 75.1 67.3 50 71.5 73.4 62.5 76 76.2 71.2 49.479.3 79.3 70.6 47.7 SAFT (° C.) 97.8 109.1 110 125.2 91.9 88.8 107.4125.5 96 109.6 121.8 95.7 88.1 108.2 120.1 92 99.4 Clarity Clear ClearClear Clear Clear Clear Clear Clear Clear Clear Clear Clear Clear ClearClear Clear Clear (177° C.)

As shown in TABLE 14, the inventive adhesives exhibited adhesiveproperties that are either comparable or superior to common adhesives inthe industry. The inventive adhesives can exhibit desirable clarity anddesirable processability as indicated by their viscosities. Furthermore,as shown in TABLE 14, the inventive adhesives can exhibit superioradhesive properties.

Example 11

Hot melt pressure-sensitive adhesives for tapes and labels were producedusing an inventive propylene-ethylene copolymer (Sample 7D from Example7). The adhesives were produced in accordance with the process describedin Example 4. The adhesives were produced with Vistamaxx™ 6202(Exxonmobil), Kraton® 1162 (Kraton), Kraton® 1657 (Kraton), Regalite™R1090 (Eastman Chemical), Kaydol mineral oil (Sonneborn), and Irganox®1010 (BASF). TABLE 15, below, describes the composition and propertiesof the inventive adhesives. It should be noted that the compositionalcomponents recited in TABLE 15 are based on weight percentage. The probetack (kg) of the adhesive was measured according to ASTM D9279 and thehold power (hours) was measured according to ASTM D3654.

TABLE 15 Adhesives IA1 IA2 IA3 Composition Sample 7D 20 20 20 ofAdhesives Vistamax ® 20 6202 Kraton ® 1161 20 Kraton ® 1657 20Regalite ™ 48.5 48.5 48.5 R1090 Mineral Oil 10.5 10.5 10.5 Irganox ®1010 1 1 1 Brookfield 14900 7200 10250 Visc. 177° C. (cps) Probe Tack0.5 0.4 0.4 (kg) Hold Power 3.5 .01 1.6 (on SS) (hours)

As shown in TABLE 15, the inventive adhesives exhibited adhesiveproperties that are either comparable or superior to common adhesives inthe industry.

Example 12

Polymer blends were produced to observe the effects that certainpolymers had on particular blends. In this example, a commercialpropylene homopolymer (Exxon™ PP3155) was compared to a propylenehomopolymer prepared in accordance with Example 1. This propylenehomopolymer (“Sample 12A”) was produced without an electron donor andhad a softening point of 157.5° C. and a needle penetration of 7 dmm.These two homopolymers were separately combined with Kraton® G1650(Kraton), Kraton® G1651 (Kraton), CaCO₃, Drakeol® 34 oil (CalumetSpecialty Products), and Kristalex™ 5140 (Eastman Chemical) to producepolymer blends. The composition and properties of these polymer blendsare depicted in TABLE 16 below. It should be noted that all compositionvalues in TABLE 16 are based on weight percentages.

Furthermore, various properties of the polymer blends were measured asshown TABLE 16. The tested properties included Shore A hardness (ASTMD2240), melt flow rate (ASTM D1238), tear strength (ASTM D624), 100%modulus (ASTM D412), 200% modulus (ASTM D412), 300% modulus (ASTM D412),elongation at break (ASTM D412), tensile strength (ASTM D412), andYoung's Modulus (ASTM E111-04).

TABLE 16 Blends Non-Commercial Commercial Composition Exxon ® 3155 (PP)15 of Blends Sample 12A 15 Kraton ® G1650 17.5 17.5 Kraton ® G1651 17.517.5 CaCO₃ 15 15 Drakeol ® 34 oil 25 25 Kristalex ™ 5140 10 10 Hardness(Shore A) 45 70 Melt Flow Rate 31.74 18.1 (22° C./5.16 kg) Tear Strength170 281 (lbf/in) 100% Modulus 209 466 200% Modulus 298 670 300% Modulus415 932 Elongation at Break 425 677 Tensile Strength 576 2785 Young'sModulus 0.324 0.67

As shown above, the non-commercial homopolymer produced using theprocess described above can improve polymer blends in a similar manneras commercial homopolymers.

The inventors hereby state their intent to rely on the Doctrine ofEquivalents to determine and assess the reasonably fair scope of thepresent invention as it pertains to any apparatus not materiallydeparting from but outside the literal scope of the invention as setforth in the following claims.

The preferred forms of the invention described above are to be used asillustration only, and should not be used in a limiting sense tointerpret the scope of the present invention. Modifications to theexemplary embodiments, set forth above, could be readily made by thoseskilled in the art without departing from the spirit of the presentinvention.

Example 13

Hot melt adhesives for hygiene and packaging applications were producedusing the inventive propylene-ethylene copolymers depicted in TABLE 17.The copolymers used to manufacture these adhesive samples were producedin accordance with the process described in Example 1. Furthermore,TABLE 17 also indicates the electron donor that was used to produce thecopolymers.

TABLE 17 Copolymer Sample 13A 13B 13C 13D 13E 13F Visc. @ 190° C., 18132063 16525 18400 19000 1840 cP Softening 133.5 130.6 110.4 115.9 117.4132.7 Point (° C.) Needle Pen. 22.8 22.7 32.8 28.1 23.6 22.8 (dmm) Wt. %Ethylene 16 16 22 21 20 16 Wt. % Propylene 84 84 78 79 80 84 ElectronDonor D D D D D D

The adhesives were produced in accordance with the process described inExample 4. The adhesives were produced with various additives includingRegalite™ R1090 (Eastman Chemical), Eastotac™ H100W (Eastman Chemical),Kaydol® mineral oil (Sonneborn), Licocene® wax (Clarient), Sasol wax H-1(Sasol), and Irganox® 1010 (BASF). TABLE 18 and TABLE 19, below,describes the composition and properties of the inventive adhesives.TABLE 18 contains inventive adhesives that can be utilized for thehygiene construction market, while TABLE 19 contains inventive adhesivesthat can be used for packaging. It should be noted that thecompositional components recited in TABLE 18 and TABLE 19 are based onweight percentage and that all components add up to 100 percent.

TABLE 18 Adhesives IA1 IA2 IA3 IA4 IA5 IA6 IA7 IA8 IA9 CA1 CA2 CA3 CA413C 40 — — 35 — — 35 — — 13D — 40 — — 35 — — 35 — 13E — — 40 — — 35 — —35 Regalite ® 48.5 48.5 48.5 46.5 46.5 46.5 46.5 46.5 46.5 R1090Kaydol ® Oil 10.5 10.5 10.5 10.5 10.5 10.5 10.5 10.5 10.5 Sasol ® H1 wax— — — 7 7 7 — — — Licocene ® 6102 — — — — — — 7 7 7 Irganox ® 1010 1 1 11 1 1 1 1 1 300 mm Peel Strength—24 Hrs at Room Temperature (SignatureNozzle Sprayed Samples) g/mm 2.64 3.17 2.63 4.62 4.51 5.1 4.64 4.03 4.861.73 4.64 4.62 3.44 Std. Dev. 0.2 0.43 0.19 0.2 0.42 0.28 0.33 0.29 0.360.17 0.19 0.37 0.23 300 mm Peel Strength—Body Temperature (SignatureNozzle Sprayed Samples) g/mm 2.83 3.34 3.27 5.08 4.81 5.58 4.45 4.524.55 1.91 4.99 4.39 3.43 Std. Dev. 0.29 0.22 0.09 0.19 0.49 0.52 0.130.39 0.52 0.12 0.2 0.17 0.05 300 mm Peel Strength—2 Weeks Aged(Signature Nozzle Sprayed Samples) g/mm 2.75 3.21 2.91 4.74 5.23 6.824.91 5.05 6.13 2.71 5.11 4.16 3.39 Std. Dev. 0.15 0.38 0.22 0.26 0.550.59 0.27 0.69 0.51 0.34 0.16 0.21 0.34 Spray 305 to 350 305 350 325 335Temperature (° F.) Brookfield Viscosity and Gardner Color Initial 16001470 1657 925 660 992 1017 1145 1102 1780 3287 2250 1617 Viscosity at177° C. (cPS) 96 hrs at 177° C. 1390 1308 1507 857 2260 910 990 1050 9752245 987 240 Aged Viscosity (cPS) Initial 1 1 1 1 1 1 1 1 1 1 1 2 8Gardner Color) 96 hrs at 177° C. 8 8 6 7 8 7 6 7 7 9 12 18 18 AgedGardner Color 300 mm Peel Strength—24 Hrs at Room Temperature (CF NozzleSprayed Samples) g/mm 5.58 5.99 6.24 8.36 8.33 10.28 9.49 9.06 9.94 Std.Dev. 0.36 0.39 0.68 0.24 0.71 0.51 0.43 0.93 0.61 300 mm PeelStrength—Body Temperature (CF Nozzle Sprayed Samples) g/mm 5.75 6.2 6.588.94 9.24 10.11 8.92 9.79 9.44 Std. Dev. 0.32 0.15 0.49 0.44 0.51 0.380.36 0.77 0.49 300 mm Peel Strength—2 Wks Aged (CF Nozzle SprayedSamples) g/mm 5.88 6.76 6.26 10.31 10.39 14.32 12.06 11.69 11.49 Std.Dev. 0.25 0.36 0.35 0.85 1.44 0.75 0.88 0.61 0.42 Spray 270 to 350Temperature (° F.)

TABLE 18, above, describes the composition and properties of theinventive adhesives, which are labeled as IA1-IA9. Comparativecommercial adhesives were also analyzed and are labeled as CA1-CA4.CA1-CA3 utilize olefin based polymers for adhesives in hygieneconstruction. CA4 is also a commercial adhesive using styrenic blockcopolymers for use in hygiene construction. The hygiene adhesives inTABLE 18 made using inventive polymers show broad operating window usingwide range of spraying/coating techniques (signature, summit, CF, omega,intermittent, sloat etc.) with excellent sprayability/coatabilitycharacteristics over a wide range of temperatures (270° F. to 350° F.)with good adhesive peel at room temperature, body temperature and underaged conditions (elevated temperature and room temperature) with anadd-on level varying from 0.5-8.0 gsm. Thermal stability, Garner colorand Brookfield viscosity stability of the adhesives made using inventivepolymers are also excellent, and the adhesives made using the inventivepolymers are clear at room temperature with no color and no odor.

The initial viscosity of the adhesives in TABLE 19 was measured at 177°C., along with the SAFT, PAFT, % fiber tear and open/set times. Agedviscosities of the adhesives were generated to determine theprocessability characteristics and long term aging stability of theadhesives. The PAFT and SAFT measurements are performed to understandthe peel adhesion and shear strength of the adhesives over a temperatureperiod in a SAFT oven. Furthermore, the initial and aged color inGardner color scale was also measured.

TABLE 19 IA10 IA11 IA12 IA13 IA14 IA15 IA17 IA18 IA19 IA20 13A 60 75 6075 13F 60 75 60 75 60 75 Regalite ® R1090 14.5 4.5 14.5 4.5 14.5 4.514.5 4.5 Eastotac ® H100W 14.5 4.5 Licocene ® 6102 24.5 19.5 24.5 19.524.5 19.5 Sasol H1 Wax 24.5 19.5 24.5 19.5 Irganox ® 1010 1 1 1 1 1 1 11 1 1 Adhesive Properties Initial Brookfield viscosity 742.5 1170 8001165 790 2640 552 935 565 930 @ 177° C. Aged (96 hrs at 177° C.) 7151070 677 1035 715 2377 445 790 452 795 Brookfield viscosity @ 177° C.Initial Gardner color 1 1 1 1 1 1 1 1 1 1 Aged Gardner color (96 hrs 8 88 8 10 7 8 7 8 6 at 177° C.) PAFT, Kraft paper (° C.) 27.2 26.5 26.726.5 32.1 31 PAFT Std. Deviation 1.3 0.1 0.4 0.4 4.3 3.6 SAFT, Kraftpaper (° C.) 123.3 70 108.7 127.3 118.5 110.8 SAFT—Std. Deviation 3.58.5 12.9 3.3 2.3 1.9 Open/Set time (sec) 40/18 32/12 35/13 32/15 32/945/17 20/25 20/27 15/20 % Fiber Tear 0° C. 100 100 100 100 100 100 0 0 00 (3x = 3 samples) (3x) (3x) (3x) (3x) (3x) (3x) (3x) (3x) (3x) (3x)Room Temperature 100 100 0 0 0 0 (3x = 3 samples) (3x) (3x) (3x) (3x)(3x) (3x) 135° C. 0 0 0 0 25 0 0.5 0 0 0 (3x = 3 samples) (3x) (3x) (3x)(3x) (3x) (3x) (3x) (3x) (3x) (3x)

What is claimed is:
 1. A copolymer comprising propylene and ethylene,wherein said copolymer has a softening point in the range of 90 to lessthan 115° C., wherein said copolymer has a needle penetration equal toor less than 53 dmm.
 2. The copolymer of claim 1, wherein said copolymercomprises in the range of 7 to 35 weight percent of ethylene.
 3. Thecopolymer of claim 1, wherein said copolymer has a Brookfield viscosityat 190° C. in the range of 500 to 30,000 cps.
 4. The copolymer of claim1, wherein said copolymer comprises in the range of 40 to 95 weightpercent of propylene.
 5. The copolymer of claim 1, wherein the weightratio of propylene to ethylene in said copolymer is in the range of 1:1to 15:1.
 6. The copolymer of claim 1, wherein said copolymer comprisesat least one C₄-C₁₀ alpha-olefin.
 7. An article comprising saidcopolymer of claim
 1. 8. An adhesive comprising said copolymer ofclaim
 1. 9. The adhesive of claim 8, wherein said adhesive comprises inthe range of 5 to 95 weight percent of said copolymer.
 10. The adhesiveof claim 8, wherein said adhesive comprises in the range of 5 to 95weight percent of at least one polymer.
 11. The adhesive of claim 8,wherein said adhesive comprises in the range of 0 to 70 weight percentof at least one tackifier.
 12. The adhesive of claim 8, wherein saidadhesive comprises in the range of 0 to 30 weight percent of at leastone processing oil.
 13. The adhesive of claim 8, wherein said adhesivecomprises in the range of 0 to 30 weight percent of at least one wax.14. The adhesive of claim 8, wherein said needle penetration is in therange of 0.5 to 70 dmm.
 15. The adhesive of claim 8, wherein the weightratio of propylene to ethylene in said copolymer is in the range of 1:1to 5:1.
 16. The adhesive of claim 8, wherein said adhesive applied atlower temperature (such as 100-145° C.) has a peel strength in the rangeof 1 to 200 g/mm, wherein said adhesive applied at higher temperature(such as 145-180° C.) has a peel strength in the range of 1 to 250 g/mm.17. The adhesive of claim 8, wherein said adhesive has a loop tack inthe range of 0.1 to 50 lbf.
 18. The adhesive of claim 8, wherein saidadhesive has an initial Gardner color of 0.1 to 18.